CN109851785A - A kind of low moisture absorption, high heat resistance type polyimides toughening polymer and preparation method thereof - Google Patents
A kind of low moisture absorption, high heat resistance type polyimides toughening polymer and preparation method thereof Download PDFInfo
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- CN109851785A CN109851785A CN201811550458.9A CN201811550458A CN109851785A CN 109851785 A CN109851785 A CN 109851785A CN 201811550458 A CN201811550458 A CN 201811550458A CN 109851785 A CN109851785 A CN 109851785A
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- aminophenyl
- benzo
- moisture absorption
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Abstract
It include constitutional repeating unit shown in formula (I) and formula (II) in the polymer molecular chain the invention discloses low moisture absorption, high heat resistance type polyimides toughening polymer.Polyimides toughening particle prepared by the present invention has the characteristics that even particle size distribution, water absorption rate are low, heat resisting temperature is high, can meet the requirement of low moisture absorption, high heat resistance simultaneously, have broad application prospects.
Description
Technical field
The invention belongs to technical field of polymer materials, and in particular to a kind of low moisture absorption, high heat resistance type polyimides toughening
Polymer and preparation method thereof.
Background technique
Fiber reinforcement thermosetting matrix resin composite material, such as carbon fiber-four-functional group epoxy resin composite material, because of it
The performance of specific strength and specific modulus etc. is prominent and obtains a large amount of application in high structural strength & lightweight demand side；But
It is that this thermoset substrate resin generally comprises the thermoplastic particles of one or more of " toughenings ", such as nylon particle and polyamide-
Acid imide superfine powder.The nylon particle of " toughening " that has been commercialized, such as 6 microballoon of nylon of Arkema company, France, brew water suction
Rate is up to 3.5%, represent can long-term use temperature heat distortion temperature (HDT, 1.82MPa) only at 100 DEG C hereinafter, temperature resistant grade
It is lower；The polyamide-imides superfine powder of " toughening " that has been commercialized, such as the Torlon 4000TF of Solvay company, Belgium,
Although represent can long-term use temperature heat distortion temperature (HDT, 1.82MPa) at 240 DEG C or more, temperature resistant grade is higher,
Brew water absorption rate is up to 4.0%.
As fiber reinforcement thermosetting matrix resin composite material is required that under the super-humid conditions higher than 177 DEG C, stabilization makes
With fiber reinforcement thermosetting matrix resin composite material manufacturing enterprise is desirable for always brew water absorption rate " increasing lower than 1.5%
It is tough " thermoplastic particles, to cooperate high heat resistance type thermoset substrate resin (such as four-functional group epoxy resin, bismaleimide
Resin, cyanate ester resin and thermoset polyimide resin etc.) stablize use under new requirement.However, these have been commercialized
The thermoplastic particles of " toughening " have been unable to meet new requirement since brew water absorption rate is high.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of low moisture absorption, high heat resistance type polyimides toughening polymer, with
Solve fiber reinforcement thermosetting matrix resin composite material in the prior art stabilization cannot make under the super-humid conditions higher than 177 DEG C
The problem of using.
The present invention also technical problems to be solved are to provide above-mentioned low moisture absorption, high heat resistance type polyimides toughening polymer
Preparation method.
The present invention will finally solve the problems, such as to be to provide above-mentioned low moisture absorption, high heat resistance type polyimides toughening polymer particle
Preparation method.
In order to solve the above technical problems, the present invention adopts the following technical scheme:
A kind of low moisture absorption, high heat resistance type polyimides toughening polymer include formula (I) and formula in the polymer molecular chain
(II) constitutional repeating unit shown in,
In formula (I), X is the divalent functional group of benzo heteroaromatic, and structural formula such as formula (A)~(E) is any shown,
Alternatively, the structure of X are as follows: 5- amino -2- (4- aminobenzene) benzoxazoles, 5- amino -2- (3- aminobenzene) benzo are disliked
Azoles, 2,6- bis- (4- aminophenyl) benzo [1,2-d；5,4-d '] dioxazole, 2,6- bis- (3- aminophenyl) benzo [1,2-d；5,
4-d '] dioxazole, 2- (3- aminophenyl) -6- (4- aminophenyl) benzo [1,2-d；5,4-d '] it is any one in dioxazole
Kind；
In formula (II), Y be benzo heteroaromatic divalent functional group, as formula (F)~(J) it is any shown in:
Alternatively, the structure of Y are as follows: 5- amino -2- (4- aminobenzene) benzimidazole, 5- amino -2- (3- aminobenzene) benzo miaow
Azoles, 2,6- bis- (4- aminophenyl) benzo diimidazole, 2,6- bis- (3- aminophenyl) benzo diimidazole, 2- (3- aminophenyl)-
Any one in 6- (4- aminophenyl) benzo diimidazole；
In formula (I) and formula (II), R is-CH3 or-CF3, and R is identical structure or different structure, X and Y be identical structure or
Different structure；M and n is natural number, and m and n are identical value or different value.
A kind of low moisture absorption, high heat resistance type polyimides toughening polymer preparation method, include the following steps:
In polar aprotic solvent, benzo heteroaromatic diamines is added, stirring and dissolving is complete at 25~50 DEG C；It drops again
Temperature is added that 4,4 '-(4,4 '-isopropyl diphenoxy) bis- (phthalic anhydrides), 4,4 '-(4,4 '-hexafluoros are different to 10~20 DEG C
Two phenoxy group of propyl) bis- (phthalic anhydrides) or both mixture, stirring polymerization 10~18 hours forms polyamic acid tree
Rouge；It is rapidly heated between 200~240 DEG C, is stirred at reflux 0.5~3 hour again, obtain the low moisture absorption, high heat resistance type polyamides Asia
Amine toughening polymer.
Wherein, the polar aprotic solvent is N- cyclohexyl pyrrolidone, N-Methyl pyrrolidone, dimethyl Asia
One or more of mixture in sulfone, isoquinolin.
Wherein, the benzo heteroaromatic diamines are as follows: 5- amino -2- (4- aminobenzene) benzoxazoles, 5- amino -2- (3- ammonia
Base benzene) benzoxazoles, 2,6- bis- (4- aminophenyl) benzo [1,2-d；5,4-d '] dioxazole, 2,6- bis- (3- aminophenyl) benzene
And [1,2-d；5,4-d '] dioxazole, 2- (3- aminophenyl) -6- (4- aminophenyl) benzo [1,2-d；5,4-d '] dioxazole,
5- amino -2- (4- aminobenzene) benzimidazole, 5- amino -2- (3- aminobenzene) benzimidazole, 2,6- bis- (4- aminophenyl) benzene
And diimidazole, 2,6- bis- (3- aminophenyl) benzo diimidazole, 2- (3- aminophenyl) -6- (4- aminophenyl) benzo diimidazole
One or both of.
Preferably, during the preparation process, the mass fraction of solid content is 5~45%
A kind of low moisture absorption, high heat resistance type polyimides toughening polymer particle preparation method, include the following steps:
(1) prepare the suspension of polyimides: polyimide resin solution mixed with poor solvent, -20~20 DEG C,
The suspension of polyimides is prepared under the conditions of 1800~7800rpm；
(2) it impregnates separation: centrifugal filtration being carried out to the suspension for the polyimides that step (1) obtains, obtains polyimides
The filter cake of particle impregnates it with poor solvent, then is centrifugated, and is repeated 3 times, and obtains the filter cake of medlin particulate；
(3) drying and grinding: being dried grinding to the filter cake for the medlin particulate that step (2) obtains, obtain low moisture absorption,
The particle of high heat resistance type polyimides toughening polymer.
Wherein, the poor solvent be acetone, methanol mixture, wherein acetone, methanol volume ratio be 1:1.
Wherein, in step (1), the volume ratio of poor solvent and polyimide resin solution is 0.5~5:1
Wherein, in step (3), the program of drying and grinding is as follows: grinding after dry 4hr at 50 DEG C, at 70 DEG C after dry 4hr
It grinds, is ground after dry 4hr at 130 DEG C, ground after dry 2hr at 180 DEG C, dry 2hr at 240 DEG C.
Beneficial effect
Polyimides toughening particle prepared by the present invention has the feature that
1) specific particle size distribution characteristic: D (05)≤1 μm, D (50)≤35 μm, (95)≤75 μm D.
2) brew Xi Shui Shuai≤1.4%.
3) heat distortion temperature (HDT, 1.82MPa) is at 260 DEG C or more.
4) Te Nian Du≤0.37dL/g.
Polyimides toughening particle prepared by the present invention can meet the requirement of low moisture absorption, high heat resistance simultaneously, have wide
Application prospect.
Specific embodiment
In the present invention preparation process of polyimides toughening particle include polymerization imidization, direct pulp, impregnate separation and
Drying and grinding Four processes.
The preparation of polyimides toughening polymer:
In high boiling polar aprotic solvent, (such as N- cyclohexyl pyrrolidone, N-Methyl pyrrolidone, dimethyl are sub-
Sulfone, isoquinolin etc. or they arbitrarily arrange in pairs or groups the mixed solvent of arbitrary proportion) in, be firstly added benzo heteroaromatic diamines, 25~
Stirring and dissolving is complete at 50 DEG C；It is cooled between 10~20 DEG C again, 4,4 '-(4,4 '-isopropyl diphenoxy) bis- (adjacent benzene is added
Dicarboxylic acid anhydride), the mixing of 4,4 '-(4,4 '-hexafluoro isopropyl, two phenoxy group) bis- (phthalic anhydrides) or their special ratios
Object, stirring polymerization 10~18 hours, forms polyamic acid resin；It is rapidly heated between 200~240 DEG C again, is stirred at reflux 0.5
~3 hours, obtain polyimide resin solution.It polymerize in imidization, selects solid content between 5~45% (Wt.).
Direct slurrying process, using (application No. is in 201821370510.8 patent applied for) slurrying device, choosing
It is poor solvent with acetone/methanol mixed solvent (V:V=1:1), poor solvent volume is polyimide resin solution volume
0.5~5.0 times；For slurrying temperature between -20~20 DEG C, pulp revolving speed prepares the suspended of polyimides in 1800~7800rpm
Liquid.
Separation process is impregnated, centrifugal filtration operation is selected to isolate the polyimides from the suspension of above-mentioned polyimides
The filter cake of particle；Selection acetone/methanol (V:V=1:1) mixed solvent is poor solvent, is impregnated to filter cake and separates behaviour again
Make, is repeated 3 times.
Drying and grinding process selects tray drying that grinding, journey is dried to the filter cake of above-mentioned polyimides toughening particle
Sequence is as follows: grinding grinding → 240 after → 180 DEG C/2hr after grinding → 130 DEG C/4hr after → 70 DEG C/4hr of grinding after 50 DEG C/4hr
℃/2hr.Grinding operation selects toothed disc type multifunctional crusher WN-200 (Hangzhou Xu Zhong mechanical equipment Co., Ltd) to carry out, often
It is secondary to crush one time.After drying and grinding, the polyimides toughening particulate samples are obtained.
The detection and test of sample
1, laser particle size measurement
Granularity is carried out to the polyimides toughening fine grain final product according to the wet process in examination criteria GB/T 19077.1-2003
Test.
2, brew water absorption rate
Plastic tab after all test samples to be made to 0.1 ± 0.01mm, according in examination criteria GB/T1034-1998
Method 3, continuous brew r for 24 hours, the brew water absorption rate of test sample.
3, heat distortion temperature
According to examination criteria GBT1634.1-2004, using 1.82MPa load, heat distortion temperature detection is carried out to sample.
4, inherent viscosity
According to examination criteria GB/T 1632.3-2010, solvent is made using NMP, selects the Ubbelohde viscosity tube of Φ 0.84mm,
Inherent viscosity detection is carried out to sample.
Embodiment 1:
Polymerize imidization, 873.70 grams of dimethyl sulfoxides/N- cyclohexyl pyrrolidone mixed solvent (V:V=3:
7) in, it is firstly added 34.235 grams of 2,6- bis- (3- aminophenyl) benzo [1,2-d；5,4-d '] dioxazole, at 25~50 DEG C
Stirring and dissolving is complete；It is cooled to 15 DEG C again, is added 62.843 gram 4,4 '-(4,4 '-hexafluoro isopropyl, two phenoxy group) bis- (adjacent benzene two
Formic anhydride), stirring polymerization 12 hours forms polyamic acid resin；It is rapidly heated again to 230 DEG C, is stirred at reflux 2 hours, obtains
Polyimide resin solution.
Direct slurrying process, it is (nonstandard according to the patent applied for application No. is 201821370510.8 in 3L slurrying device
Production) in, selecting acetone/methanol mixed solvent (V:V=1:1) is poor solvent, and poor solvent volume is polyimide resin
1.5 times of liquor capacity；For slurrying temperature at -10 DEG C, pulp revolving speed prepares the suspension of polyimides in 6000rpm.
Separation process is impregnated, centrifugal filtration operation is selected to isolate the polyimides from the suspension of above-mentioned polyimides
The filter cake of particle；Selecting acetone/methanol mixed solvent (V:V=1:1) is poor solvent, is impregnated to filter cake and separates behaviour again
Make, in triplicate.
Drying and grinding process selects tray drying that grinding, journey is dried to the filter cake of above-mentioned polyimides toughening particle
Sequence is as follows: grinding grinding → 240 after → 180 DEG C/2hr after grinding → 130 DEG C/4hr after → 70 DEG C/4hr of grinding after 50 DEG C/4hr
℃/2hr.Grinding operation selects toothed disc type multifunctional crusher (many mechanical WN-200 of the Hangzhou rising sun) to carry out, and crushes one time every time
?.After drying and grinding to get arrive the polyimides toughening particulate samples.
Sample carries out performance detection or test according to aforementioned examination criteria.
Embodiment 2:
In addition to formula, the preparation process of polyimides toughening particle is identical with embodiment 1 in the present embodiment.This reality
The formula for applying example is as follows: 767.42 grams of (V:V=3:7's) dimethyl sulfoxides/N- cyclohexyl pyrrolidone mixed solvent, and 22.426
Gram 5- amino -2- (3- aminobenzene) benzimidazole, 62.843 gram 4,4 '-(4,4 '-hexafluoro isopropyl, two phenoxy group) bis- (adjacent benzene two
Formic anhydride).
Sample carries out performance detection or test according to aforementioned examination criteria.
Embodiment 3:
In addition to formula, the preparation process of polyimides toughening particle is identical with embodiment 1 in the present embodiment.This reality
The formula for applying example is as follows: 774.57 grams of (V:V=3:7's) dimethyl sulfoxides/N- cyclohexyl pyrrolidone mixed solvent, and 34.014
Gram 2- (3- aminophenyl) -6- (4- aminophenyl) benzo diimidazole, 52.049 gram 4,4 '-(4,4 '-isopropyl diphenoxies)
Bis- (phthalic anhydrides).
Product carries out performance detection or test according to aforementioned examination criteria.
Embodiment 4:
In addition to formula, the preparation process of polyimides toughening particle is identical with embodiment 1 in the present embodiment.This reality
The formula for applying example is as follows: 718.85 grams (V: V=3: 7) dimethyl sulfoxide/N- cyclohexyl pyrrolidone mixed solvent, 22.426
Gram 5- amino -2- (3- aminobenzene) benzimidazole, 31.422 gram 4,4 '-(4,4 '-hexafluoro isopropyl, two phenoxy group) bis- (adjacent benzene two
Formic anhydride) and 26.024 gram 4, the mixture of 4 '-(4,4 '-isopropyl diphenoxy) bis- (phthalic anhydrides).
Product carries out performance detection or test according to aforementioned examination criteria.
Embodiment 5:
In addition to formula, the preparation process of polyimides toughening particle is identical with embodiment 1 in the present embodiment.This reality
The formula for applying example is as follows: 823.14 grams (V: V=3: 7) dimethyl sulfoxide/N- cyclohexyl pyrrolidone mixed solvent, 34.014
Gram 2- (3- aminophenyl) -6- (4- aminophenyl) benzo diimidazole, 31.422 gram 4,4 '-(4,4 '-hexafluoro isopropyl hexichol oxygen
Base) bis- (phthalic anhydrides) and 26.024 gram 4, the mixing of 4 '-(4,4 '-isopropyl diphenoxy) bis- (phthalic anhydrides)
Object.
Sample carries out performance detection or test according to aforementioned examination criteria.
In the invention patent, 6 microballoon of nylon being commercialized is selected (such as1002D etc.) as a comparison case 1 sample
Product, select the polyamide-imides superfine powder (such as Torlon 4000TF) that has been commercialized as a comparison case 2 sample.Sample
Performance detection or test are carried out also according to aforementioned examination criteria.
The properties of sample of all embodiment and comparative examples detects or test result is as described in Table 1.
From table 1 it follows that the invention patent successfully provides a kind of low moisture absorption & high heat resistance type polyimides toughening
Particle is required that in the case where being higher than 177 DEG C of super-humid conditions, stabilization makes with fiber reinforcement thermosetting matrix resin composite material is met
With desired outstanding properties.
1 testing result of table
Claims (9)
1. a kind of low moisture absorption, high heat resistance type polyimides toughening polymer, which is characterized in that include formula in the polymer molecular chain
(I) and constitutional repeating unit shown in formula (II),
In formula (I), X is the divalent functional group of benzo heteroaromatic, and structural formula such as formula (A)~(E) is any shown,
Alternatively, the structure of X are as follows: 5- amino -2- (4- aminobenzene) benzoxazoles, 5- amino -2- (3- aminobenzene) benzoxazoles, 2,
6- bis- (4- aminophenyl) benzo [1,2-d；5,4-d '] dioxazole, 2,6- bis- (3- aminophenyl) benzo [1,2-d；5,4-d']
Dioxazole, 2- (3- aminophenyl) -6- (4- aminophenyl) benzo [1,2-d；5,4-d '] any one in dioxazole；
In formula (II), Y be benzo heteroaromatic divalent functional group, as formula (F)~(J) it is any shown in:
Alternatively, the structure of Y are as follows: 5- amino -2- (4- aminobenzene) benzimidazole, 5- amino -2- (3- aminobenzene) benzimidazole, 2,
6- bis- (4- aminophenyl) benzo diimidazole, 2,6- bis- (3- aminophenyl) benzo diimidazole, 2- (3- aminophenyl) -6- (4-
Aminophenyl) any one in benzo diimidazole；
In formula (I) and formula (II), R is-CH3 or-CF3, and R is identical structure or different structure, and X and Y are identical structure or difference
Structure；M and n is natural number, and m and n are identical value or different value.
2. the preparation method of low moisture absorption described in claim 1, high heat resistance type polyimides toughening polymer, which is characterized in that packet
Include following steps:
In polar aprotic solvent, benzo heteroaromatic diamines is added, stirring and dissolving is complete at 25~50 DEG C；It is cooled to again
10~20 DEG C, 4,4 '-(4,4 '-isopropyl diphenoxy) bis- (phthalic anhydrides), 4,4 '-(4,4 '-hexafluoro isopropyls are added
Two phenoxy groups) bis- (phthalic anhydrides) or both mixture, stirring polymerization 10~18 hours forms polyamic acid resin；
It is rapidly heated between 200~240 DEG C, is stirred at reflux 0.5~3 hour again, obtain the low moisture absorption, high heat resistance type polyimides increases
Tough polymer.
3. according to claim 2 low moisture absorption, high heat resistance type polyimides toughening polymer preparation method, feature exists
In the polar aprotic solvent is N- cyclohexyl pyrrolidone, in N-Methyl pyrrolidone, dimethyl sulfoxide, isoquinolin
One or more of mixtures.
4. according to claim 2 low moisture absorption, high heat resistance type polyimides toughening polymer preparation method, feature exists
In the benzo heteroaromatic diamines are as follows: 5- amino -2- (4- aminobenzene) benzoxazoles, 5- amino -2- (3- aminobenzene) benzo are disliked
Azoles, 2,6- bis- (4- aminophenyl) benzo [1,2-d；5,4-d '] dioxazole, 2,6- bis- (3- aminophenyl) benzo [1,2-d；5,
4-d '] dioxazole, 2- (3- aminophenyl) -6- (4- aminophenyl) benzo [1,2-d；5,4-d '] dioxazole, 5- amino -2-
(4- aminobenzene) benzimidazole, 5- amino -2- (3- aminobenzene) benzimidazole, 2,6- bis- (4- aminophenyl) benzo diimidazole,
One of 2,6- bis- (3- aminophenyl) benzo diimidazole, 2- (3- aminophenyl) -6- (4- aminophenyl) benzo diimidazole
Or two kinds.
5. according to claim 2 low moisture absorption, high heat resistance type polyimides toughening polymer preparation method, feature exists
During the preparation process, the mass fraction of solid content is 5~45%
6. a kind of low moisture absorption, high heat resistance type polyimides toughening polymer particle preparation method, which is characterized in that including such as
Lower step:
(1) it prepares the suspension of polyimides: polyimide resin solution being mixed with poor solvent, in -20~20 DEG C, 1800
The suspension of polyimides is prepared under the conditions of~7800rpm；
(2) it impregnates separation: centrifugal filtration being carried out to the suspension for the polyimides that step (1) obtains, obtains medlin particulate
Filter cake, it is impregnated with poor solvent, then is centrifugated, is repeated 3 times, the filter cake of medlin particulate is obtained；
(3) drying and grinding: being dried grinding to the filter cake for the medlin particulate that step (2) obtains, and obtains low moisture absorption, high resistance to
The particle of heat type polyimides toughening polymer.
7. according to claim 6 low moisture absorption, high heat resistance type polyimides toughening polymer particle preparation method, it is special
Sign is, the poor solvent is the mixture of acetone, methanol, wherein acetone, methanol volume ratio be 1:1.
8. according to claim 6 low moisture absorption, high heat resistance type polyimides toughening polymer particle preparation method, it is special
Sign is, in step (1), the volume ratio of poor solvent and polyimide resin solution is 0.5~5:1
9. according to claim 6 low moisture absorption, high heat resistance type polyimides toughening polymer particle preparation method, it is special
Sign is that in step (3), the program of drying and grinding is as follows: it grinds after dry 4hr at 50 DEG C, is ground after dry 4hr at 70 DEG C,
It grinds after dry 4hr at 130 DEG C, is ground after dry 2hr at 180 DEG C, dry 2hr at 240 DEG C.
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| CN110491958A (en) * | 2019-08-21 | 2019-11-22 | 深圳先进技术研究院 | Flexible substrate and preparation method thereof for thin-film solar cells |
| CN110643040A (en) * | 2019-09-03 | 2020-01-03 | 武汉华星光电半导体显示技术有限公司 | Polyimide precursor, polyimide film formed therefrom, and method for preparing the polyimide film |
| CN110747648A (en) * | 2019-11-22 | 2020-02-04 | 哈尔滨工业大学 | Carbon fiber polyimide sizing agent and preparation method and application thereof |
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| CN108117653A (en) * | 2016-11-30 | 2018-06-05 | 桂林电器科学研究院有限公司 | A kind of dimensionally stable Xing oxazolyl Kaptons and preparation method thereof |
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| CN105778130A (en) * | 2016-03-18 | 2016-07-20 | 西北工业大学 | High-strength high-heat-resistance polyimide microporous thin film and preparation method thereof |
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| CN110491958A (en) * | 2019-08-21 | 2019-11-22 | 深圳先进技术研究院 | Flexible substrate and preparation method thereof for thin-film solar cells |
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| WO2021042497A1 (en) * | 2019-09-03 | 2021-03-11 | 武汉华星光电半导体显示技术有限公司 | Polyimide precursor, polyimide film formed therefrom, and polyimide film preparation method |
| CN110747648A (en) * | 2019-11-22 | 2020-02-04 | 哈尔滨工业大学 | Carbon fiber polyimide sizing agent and preparation method and application thereof |
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